CN110880620A - Composite solid electrolyte and preparation method thereof, solid lithium battery and preparation method thereof - Google Patents
Composite solid electrolyte and preparation method thereof, solid lithium battery and preparation method thereof Download PDFInfo
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- CN110880620A CN110880620A CN201910993115.8A CN201910993115A CN110880620A CN 110880620 A CN110880620 A CN 110880620A CN 201910993115 A CN201910993115 A CN 201910993115A CN 110880620 A CN110880620 A CN 110880620A
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- polycaprolactone
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- 239000002131 composite material Substances 0.000 title claims abstract description 111
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 102
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007787 solid Substances 0.000 title claims description 32
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 46
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 45
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 36
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 239000002223 garnet Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 53
- -1 polyethylene Polymers 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000002225 Li5La3Ta2O12 Substances 0.000 claims description 7
- 229910010712 Li5La3Ta2O12 Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 4
- 229910003576 Sr0.5Ba0.5 Inorganic materials 0.000 claims description 4
- 229910010252 TiO3 Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000002224 Li5La3Nb2O12 Substances 0.000 claims description 3
- 229910010709 Li5La3Nb2O12 Inorganic materials 0.000 claims description 3
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920000573 polyethylene Polymers 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000037427 ion transport Effects 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 4
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910006270 Li—Li Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000475 Poly(ethylene oxide)-block-polycaprolactone Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the technical field of solid-state lithium batteries, and particularly provides a composite solid-state electrolyte and a preparation method thereof, and a solid-state lithium battery and a preparation method thereof. The preparation method comprises the following steps: dissolving at least one polymer of polycaprolactone and polycaprolactone derivatives and lithium salt in an organic solvent to obtain a first solution; adding garnet oxide into the first solution, and uniformly mixing to obtain a second solution; and casting and drying the second solution to obtain the composite solid electrolyte. The preparation method has the characteristics of simple process, low energy consumption, no pollution, low price and the like; more importantly, the obtained composite electrolyte has the characteristics of high ionic conductivity, electrochemical window larger than 4.5V, high ion transference number, small interface resistance, good mechanical property and the like.
Description
Technical Field
The invention belongs to the technical field of solid-state lithium batteries, and particularly relates to a composite solid-state electrolyte and a preparation method thereof, and a solid-state lithium battery and a preparation method thereof.
Background
The solid-state lithium battery has the advantages of high energy density, good safety, high working voltage, no safety problem of liquid electrolyte due to high temperature and the like, thereby having great application prospect in numerous fields. A critical component in solid state lithium batteries is the solid state electrolyte, which is generally required to have high ionic conductivity at a stable operating voltage and operating temperature.
Common solid electrolytes are mainly classified into two types: inorganic ceramic solid electrolytes and organic polymer solid electrolytes. Among them, inorganic ceramic electrolytes include sulfides, oxides, hydrides, borides and phosphides, which have the following advantages: (1) the safety is good, the combustion is not carried out, the structure is stable, the corrosion is avoided, and the leakage is avoided; (2) no volume expansion and no gas generation; (3) the working temperature is wide, the ionic conductivity and the electrochemical stability are good within the working temperature range, the working can be carried out in an extreme environment, and the method has great significance in certain fields; (4) the electrochemical stability window is wide, the decomposition voltage is high, and the electrochemical stability window can be matched with a high-voltage electrode, so that the energy density of the battery can be improved; (5) the compactness is high, the mechanical strength is large, and the short circuit problem caused by lithium dendrites can be effectively inhibited, so that lithium metal can be directly used as a negative electrode, and the energy density of the battery can be obviously improved; (6) the cycle life is longer; (7) the preparation process is simple and the price is low. However, the inorganic ceramic electrolyte has the following disadvantages: (1) the rigidity is fragile, the flexibility is poor, and the preparation difficulty of the solid lithium battery is high; (2) the thickness is large, and a very thin ceramic plate is not easy to obtain; (3) the grain boundary resistance and the interface resistance are relatively large.
The organic polymer solid electrolyte is obtained by compounding a polymer and a lithium salt, wherein the polymer generally has a low glass transition temperature and has a high lithium ion conductivity above the glass transition temperature. Common polymers include polyethylene oxide (PEO), Polyacrylonitrile (PAN), Polymethacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP).
The polymer solid lithium ion battery has the following advantages: (1) liquid electrolyte is not used, so that the problem of liquid leakage is avoided; (2) the electrolyte can be used as an electrolyte and a diaphragm, so that the overall quality of the battery can be reduced; (3) the decomposition temperature is high, the combustion is difficult, and the safety is good; (4) the lithium iron phosphate has certain mechanical strength, and can inhibit the formation of lithium dendrites to a certain extent; (5) the flexible battery has good flexibility, can be assembled, and can still work normally under the action of certain external force and deformation; (6) the preparation process is simple and easy to assemble; (7) the shape, size and thickness of the battery are all controllable, and the battery with any shape, size and thickness can be prepared. However, the polymer solid electrolyte has the following problems: (1) the mechanical strength of the polymers still needs to be further improved; (2) the ionic conductivity is low, and further improvement of the ionic conductivity is required. (3) The polymers have a high degree of crystallinity at room temperature.
Inorganic ceramic electrolytes and organic polymer electrolytes have advantages and disadvantages, but all requirements of people on solid electrolytes are difficult to meet. A composite solid electrolyte obtained by uniformly dispersing inorganic particles in a polymer can combine the advantages of both and is therefore highly preferred. The inorganic particles in the composite solid electrolyte can reduce the crystallinity of the polymer and improve the mechanical strength of the composite electrolyte. In addition, the high concentration of lithium ions in the inorganic particles can seep into the polymer electrolyte, so that the lithium ion concentration of the composite electrolyte is improved, and the ionic conductivity of the composite electrolyte is improved.
The most studied composite solid electrolytes to date are mainly polyethylene oxide (PEO) -based composite solid electrolytes. For example, the patent publication No. CN104241686A discloses an all-solid-state electrolyte obtained by a blending method of polyethylene oxide, inorganic filler and lithium salt; CN101183727 discloses lithium salt, polyethylene oxide (PEO)) The solid electrolyte is obtained by compounding the superfine powder filler; CN109119691A discloses a solid polymer composite electrolyte composed of polyethylene oxide, lithium salt and quasi-one-dimensional inorganic fast ion conductor. In addition, the Nano Energy,2018,46,176-184 reports the preparation of a composite all-state electrolyte by uniformly mixing an inorganic filler garnet oxide (LLZTO), polyethylene oxide and a lithium salt; journal of Powersources,2014,263,52-58 reports as Al2O3Polyethylene oxide and lithium salt were mixed to prepare a solid electrolyte. Although the above patents and documents use inorganic substances as fillers to improve the ionic conductivity and mechanical properties of the electrolyte, PEO has a low decomposition voltage, and thus has a problem of decomposition when matching high voltage positive electrode materials; at the same time, the lithium ion battery has smaller ion transference number and lithium salt dissolving capacity, and cannot effectively utilize lithium salt and prepare high-concentration electrolyte.
Disclosure of Invention
Aiming at the problems of low decomposition voltage, small ion migration number, poor lithium salt dissolving capacity and the like of the polyethylene oxide-based composite solid electrolyte, the invention provides the composite solid electrolyte and the preparation method thereof.
Further, a solid lithium battery using the composite solid electrolyte as an electrolyte and a preparation method of the solid lithium battery are also provided.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of preparing a composite solid electrolyte comprising the steps of:
dissolving at least one polymer of polycaprolactone and polycaprolactone derivatives and lithium salt in an organic solvent to obtain a first solution;
adding garnet oxide into the first solution, and uniformly mixing to obtain a second solution;
and casting and drying the second solution to obtain the composite solid electrolyte.
Correspondingly, the composite solid electrolyte comprises the following components in percentage by mass, based on 100% of the total mass of the components of the composite solid electrolyte:
10 to 90 percent of polymer;
5 to 80 percent of lithium salt;
garnet oxide 2% -80%;
the polymer is at least one of polycaprolactone and a polycaprolactone derivative.
Further, the solid-state lithium battery comprises a positive plate, a negative plate and a solid-state electrolyte between the positive plate and the negative plate, wherein the solid-state electrolyte is the composite solid-state electrolyte prepared by the preparation method of the composite solid-state electrolyte or the composite solid-state electrolyte.
A method for preparing a solid-state lithium battery comprises the following steps: preparing the composite solid electrolyte into a solution, coating the composite solid electrolyte solution on the surface of the positive plate by a blade coating method, drying to obtain the positive plate attached with the composite solid electrolyte, and finally assembling the positive plate and the negative plate into a solid lithium battery;
or preparing the composite solid electrolyte into a solution, coating the composite solid electrolyte solution on the surface of the negative plate by a blade coating method, drying to obtain the negative plate attached with the composite solid electrolyte, and finally assembling the negative plate and the positive plate into the solid lithium battery.
The invention has the technical effects that:
compared with the prior art, the preparation method of the composite solid electrolyte has the advantages of simple preparation process, low energy consumption, no pollution and low price; more importantly, the obtained composite electrolyte has the characteristics of high ionic conductivity, electrochemical window larger than 4.5V (high decomposition voltage), high ion transference number, small interface resistance, good mechanical property and the like.
The composite solid electrolyte has ion conductivity up to 10-5～10-3S/cm, wide electrochemical stability window, ion transference number as high as 0.4-0.7, good interface contact, small impedance, good mechanical performance and the like.
The solid electrolyte used by the solid lithium battery provided by the invention is the composite solid electrolyte provided by the invention, so that the solid lithium battery has the characteristics of high ionic conductivity, high ion transference number, wide electrochemical stability window, good interface contact, small interface resistance, high battery cycling stability, good rate capability and the like.
According to the preparation method of the solid-state lithium battery, the solid-state electrolyte layer is directly formed on the surface of the positive plate or the negative plate in a blade coating mode, the preparation process is simple, and the consistency of the battery performance is good.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a stress-strain curve of a composite solid electrolyte prepared in example 1 of the present invention.
Fig. 2 is an ac impedance curve of the composite solid electrolyte prepared in example 1 at various temperatures.
Fig. 3 is an ion conductivity of the composite solid electrolyte prepared in example 1 at various temperatures.
FIG. 4 is a polarization curve (inset is AC impedance curve before and after polarization) at 60 ℃ of the composite solid electrolyte prepared in example 1.
Fig. 5 is a linear sweep voltammogram at 60 ℃ of the composite solid electrolyte prepared in example 1.
Fig. 6 is a graph of Li-Li symmetric battery performance at different current densities at 60 ℃ for the composite solid-state electrolyte prepared in example 1.
Fig. 7 is a long cycle performance of 0.5C at 60C of the battery of application example 1.
Fig. 8 is the rate performance at 60 ℃ of the battery of application example 1.
Fig. 9 is a long cycle performance at 60 ℃ of 0.5C for the battery of application example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a composite solid electrolyte, which comprises the following steps:
dissolving at least one polymer of polycaprolactone and polycaprolactone derivatives and lithium salt in an organic solvent to obtain a first solution;
adding garnet oxide into the first solution, and uniformly mixing to obtain a second solution;
and casting and drying the second solution to obtain the composite solid electrolyte.
The above-mentioned preparation method is explained in detail below.
The related polycaprolactone derivative is at least one of polystyrene-polycaprolactone, polyoxyethylene-polycaprolactone, polyvinylidene fluoride-polycaprolactone, polyacrylonitrile-polycaprolactone, perfluoropolyether-polycaprolactone, polymethacrylic acid-polycaprolactone and polydimethylsiloxane-polycaprolactone.
The lithium salt is selected from at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium hexafluorophosphate, lithium trifluoro methyl sulfonate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluoro oxalate borate and lithium bis (oxalate) borate.
The garnet oxide is selected from Li7La3Zr2O12、Li5La3Ta2O12、Li6BaLa2Ta2O12、Li6.4La3Zr1.4Ta0.6O12、Li6Sr0.5Ba0.5La2Ta2O12、Li3Tb3Te2O12、Li5La3Ta2O12、Li0.3La0.557TiO3、Li7La3Nb2O12、Li5La3Nb2O12、Li3Ln3Te2O12At least one of (1).
In the preparation process, the mass of the obtained composite solid electrolyte is 100%, and the percentage contents of the added polymer, lithium salt and garnet oxide are as follows: 10 to 90 percent of polymer; 5 to 80 percent of lithium salt; garnet oxide 2-80%.
Such as may be:
10% of a polymer; 80% of lithium salt; 10% of garnet oxide;
or 15% of a polymer; 80% of lithium salt; 5% of garnet oxide;
or 20% of a polymer; 70% of lithium salt; 10% of garnet oxide;
or 30% of a polymer; 30% of lithium salt; 40% of garnet oxide;
or polymer 40%; 50% of lithium salt; 10% of garnet oxide;
or 50% of a polymer; 30% of lithium salt; 20% of garnet oxide;
or polymer 60%; 20% of lithium salt; 20% of garnet oxide;
or 70% of a polymer; 15% of lithium salt; 15% of garnet oxide;
or 80% of a polymer; 5% of lithium salt; 15% of garnet oxide;
or polymer 90%; 5% of lithium salt; 5% of garnet oxide;
or 18% of a polymer; 80% of lithium salt; 2% of garnet oxide;
or 15% of a polymer; 5% of lithium salt; garnet oxide 80%, and the like.
The organic solvent for dissolving the polymer, lithium salt and garnet oxide is preferably at least one of acetonitrile, tetrahydrofuran, N-dimethylformamide, succinonitrile, dichloromethane, acetone and N-methylpyrrolidone. The amount of the organic solvent to be added is not particularly limited as long as the polymer, lithium salt and garnet oxide can be completely dissolved.
The composite solid electrolyte can be cast on the surface of a container during casting, so that the obtained composite solid electrolyte has good surface flatness and uniform thickness, and can be cast on the surface of a polytetrafluoroethylene plate or the surface of a polytetrafluoroethylene container and the like.
After casting, the drying temperature is 45-150 ℃, and the drying time is 12-72 h. In order to avoid side reactions and the like of the composite solid electrolyte in the drying process, the drying can be carried out under vacuum conditions, for example, the drying can be carried out in a vacuum drying oven.
The preparation method has the advantages of simple process, low energy consumption, no pollution and low price; more importantly, the obtained composite electrolyte has the characteristics of high ionic conductivity, electrochemical window larger than 4.5V (high decomposition voltage), high ion transference number, small interface resistance, good mechanical property and the like.
Thus, the present invention provides a composite solid electrolyte. The composite solid electrolyte comprises the following components by mass percent with the total mass of 100 percent:
10 to 90 percent of polymer;
5 to 80 percent of lithium salt;
garnet oxide 2% -80%;
the polymer is at least one of polycaprolactone derivatives. The composite solid electrolyte has an ion conductivity of (10)-5～10-3) S/cm, ion transport number of 0.4-0.7, electrochemical window > 4.5V, and small interface resistance.
The composite solid electrolyte has the characteristics, so the composite solid electrolyte can be used as an electrolyte of a solid lithium battery, the thickness of a solid electrolyte membrane of the solid lithium battery is 5 mu m-4 cm, and a positive electrode and a negative electrode of the solid lithium battery are common materials in the field of solid lithium batteries, and the details are not repeated.
Specifically, a solid-state lithium battery may be prepared by:
preparing the composite solid electrolyte provided by the invention into a solution, coating the composite solid electrolyte solution on the surface of a positive plate by a blade coating method, drying to obtain the positive plate attached with the composite solid electrolyte, and finally assembling the positive plate and a negative plate into a solid lithium battery;
or, the composite solid electrolyte provided by the invention is prepared into a solution, the composite solid electrolyte solution is coated on the surface of the negative plate by a blade coating method, the negative plate attached with the composite solid electrolyte is obtained by drying treatment, and finally the negative plate and the positive plate are assembled into the solid lithium battery.
In order to more effectively understand the technical scheme of the invention, a plurality of specific embodiments are described below.
Example 1
A preparation method of a composite solid electrolyte comprises the following steps:
s11, dissolving 1g of Polycaprolactone (PCL) and 0.25g of LiFSI in an acetonitrile solvent, and uniformly mixing to obtain a first solution.
S12, mixing 0.139g of Li6.4La3Zr1.4Ta0.6O12Adding the mixture into the first solution obtained in the step S11, and uniformly mixing to obtain a second solution.
S13, casting the second solution obtained in the step S12 in a polytetrafluoroethylene container, and then placing the container in a vacuum drying oven to dry for 12 hours at 80 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 1 was tested for mechanical properties, alternating current impedance and ionic conductivity, electrochemical window and ion transport number, wherein:
(1) stress-strain curve: the results of the test using the conventional stress-strain measurement method are shown in fig. 1.
As can be seen from fig. 1, when the strain reaches 80%, the composite solid electrolyte still maintains an intact structure, and no cracks occur, which indicates that the mechanical properties are strong, and can effectively inhibit lithium dendrites.
(2) Ac impedance and ionic conductivity: the electrolyte was sandwiched between two pieces of stainless steel and placed in a 2032 type cell housing. Measured by electrochemical ac impedance spectroscopy, using the formula: where d is the thickness of the electrolyte, S is the area of the stainless steel sheet, and R is the measured impedance, the test results are shown in fig. 2.
As can be seen from FIG. 2, the resistance value at 60 ℃ is small. According to the AC impedance, the ionic conductivity at different temperatures is obtained, specifically as shown in FIG. 3, at 60 deg.C, compoundingThe ionic conductivity of the solid electrolyte was 2.3X 10-4S/cm。
(3) Ion transport number test: two lithium metal sheets are used for clamping an electrolyte to assemble an electrode, a polarized voltage of 10mV is applied to the electrode through a chronoamperometric test carried out by an electrochemical workstation, and impedance changes before and after the test are recorded. By the formula tLi +＝Is(ΔV-IiRi)/Ii(ΔV-IsRs) Wherein, IsIs a steady-state current, IiIs an initial current, RiFor testing the front interface impedance, RsFor the interface impedance after the test, Δ V is the polarization voltage, and the results are shown in fig. 4.
As can be seen from fig. 4, the ion transport number t is 0.599.
(4) Electrochemical window test: stainless steel is used as a working positive electrode, metal lithium is used as a counter electrode and a reference electrode, a solid electrolyte is clamped between the working positive electrode and the reference electrode to assemble the battery, an LSV (local Strand Va) test is carried out through an electrochemical workstation, and the test voltage range of the linear sweep voltammetry test is from open circuit voltage to 7.0V (vs Li)+/Li), scan rate of 5mVs-1The results are shown in FIG. 5.
As can be seen from fig. 5, the decomposition voltage is 5V.
The composite solid electrolyte obtained in example 1 was fabricated into a Li-Li symmetric battery, and the performance of the symmetric battery was measured at different current densities, and the results are shown in fig. 6.
As can be seen from FIG. 6, the symmetric cell can still work well without lithium dendrites after 2000h at a current density of 0.1 mA/cm; and at the current density of 0.50mA/cm, the battery is short-circuited after less than 600 hours.
Example 2
A preparation method of a composite solid electrolyte comprises the following steps:
s21, dissolving 1g of Polycaprolactone (PCL) and 0.5g of LiFSI in a tetrahydrofuran solvent, and uniformly mixing to obtain a first solution.
S22, mixing 0.22g of Li5La3Ta2O12Adding the mixture into the first solution obtained in the step S21, and uniformly mixing to obtain a second solution.
S23, casting the second solution obtained in the step S22 in a polytetrafluoroethylene plate, and then placing the polytetrafluoroethylene plate in a vacuum drying oven to dry for 15 hours at 60 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 2 was subjected to the corresponding performance test in accordance with the test method of example 1. The ion conductivity of the composite solid electrolyte is detected to be 1.5 multiplied by 10 at 60 DEG C-4S/cm, the decomposition voltage is 4.7V, and the ion transport number is 0.543.
Example 3
A preparation method of a composite solid electrolyte comprises the following steps:
s31, dissolving 0.9g of polystyrene-polycaprolactone (PS-PCL) and 0.3g of LiFSI in a tetrahydrofuran solvent, and uniformly mixing to obtain a first solution.
S32, mixing 0.3g of Li6Sr0.5Ba0.5La2Ta2O12Adding the mixture into the first solution obtained in the step S31, and uniformly mixing to obtain a second solution.
S33, casting the second solution obtained in the step S32 in a polytetrafluoroethylene container, and then placing the container in a vacuum drying oven to dry for 12 hours at 60 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 3 was subjected to the corresponding performance test in accordance with the test method of example 1. The ion conductivity of the composite solid electrolyte is detected to be 1.7 multiplied by 10 at 60 DEG C-4S/cm, the decomposition voltage was 4.9V, and the ion transport number was 0.509.
Example 4
A preparation method of a composite solid electrolyte comprises the following steps:
s41, mixing 0.6g of polyoxyethylene-polycaprolactone (PEO-PCL) and 0.25g of LiClO4Dissolving in acetonitrile solvent, and mixing to obtain a first solution.
S42, mixing 0.1g of Li7La3Zr2O12Adding the mixture into the first solution obtained in the step S41, and uniformly mixing to obtain a second solution.
S43, casting the second solution obtained in the step S42 in a polytetrafluoroethylene container, and then placing the container in a vacuum drying oven to dry for 32 hours at 75 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 4 was subjected to the corresponding performance test in accordance with the test method of example 1. The ion conductivity of the composite solid electrolyte is detected to be 4.8 multiplied by 10 at 60 DEG C-4S/cm, the decomposition voltage is 4.5V, and the ion transport number is 0.489.
Example 5
A preparation method of a composite solid electrolyte comprises the following steps:
s51, mixing 1g of perfluoropolyether-polycaprolactone (PFPE-PCL) and 0.5g of LiBF4Dissolving in N, N-dimethyl amide solvent, and mixing to obtain a first solution.
S52. adding 0.25g of Li0.3La0.557TiO3Adding the mixture into the first solution obtained in the step S51, and uniformly mixing to obtain a second solution.
S53, casting the second solution obtained in the step S52 in a polytetrafluoroethylene container, and then placing the container in a vacuum drying oven to dry for 12 hours at 100 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 5 was subjected to the corresponding performance test in accordance with the test method of example 1. The ion conductivity of the composite solid electrolyte is detected to be 2.1 multiplied by 10 at 60 DEG C-4S/cm, the decomposition voltage was 5.1V, and the ion transport number was 0.658.
Example 6
A preparation method of a composite solid electrolyte comprises the following steps:
s61, mixing 1.5g of poly (methacrylic acid) -polycaprolactone (PMMA-PCL) and 0.3g of LiClO4Dissolving in succinonitrile solvent, and mixing to obtain a first solution.
S62. adding 0.1g of Li6.4La3Zr1.4Ta0.6O12Adding the mixture into the first solution obtained in the step S61, and uniformly mixing to obtain a second solution.
S63, casting the second solution obtained in the step S62 in a polytetrafluoroethylene container, and then placing the container in a vacuum drying oven to dry for 12 hours at 100 ℃ to obtain the composite solid electrolyte.
The composite solid electrolyte obtained in example 6 was subjected to the corresponding performance test in accordance with the test method of example 1. The ion conductivity of the composite solid electrolyte is detected to be 2.1 multiplied by 10 at 60 DEG C-4S/cm, the decomposition voltage is 4.8V, and the ion transport number is 0.622.
Application example 1
A solid lithium battery is prepared by preparing the composite solid electrolyte obtained in the embodiment 1 into a solution and coating the solution on lithium iron phosphate (LiFePO)4) And (3) forming a composite solid electrolyte membrane with the thickness of 100 mu m on the positive plate, volatilizing the solvent, and then attaching a lithium metal sheet on the membrane to prepare the solid lithium battery.
Fig. 7 is a long cycle curve diagram of 0.5C at 60C for the solid-state lithium battery of application example 1, and it can be seen from fig. 7 that the battery capacity retention rate is still at least 66.7% after 1000 cycles.
Fig. 8 is the rate capability of the solid-state lithium battery of application example 1 at 60 ℃, and it can be seen from fig. 8 that the specific capacity can still maintain 66.4% of the capacity of 0.1C at a current density of 2.0C; when the current returns to 0.1C again, the specific capacity of 149.1mAh/g of the battery can still be maintained.
Application example 2
A solid lithium battery is prepared by preparing the composite solid electrolyte of example 2 into a solution and then coating the solution on lithium iron manganese phosphate (LiFe)xMn1-xPO4) And (3) forming a composite electrolyte membrane with the thickness of 150 mu m on the positive plate, volatilizing the solvent, and then attaching a lithium metal sheet on the membrane to prepare the solid lithium battery.
Fig. 9 is a long cycle curve diagram of 0.5C at 60C for the solid-state lithium battery of application example 2, and it can be seen from fig. 9 that the battery capacity hardly decays and the capacity retention rate reaches 99.9% or more after 100 cycles.
Application example 3
A solid lithium cell was prepared by preparing the composite solid electrolyte of example 3 into a solution and then knife-coating it on a graphite (C) negative electrode sheet to form a 150 μm thick composite electrolyte membrane, volatilizing the solvent, and then pasting lithium cobaltate (LiCoO) on the membrane4) And (5) preparing the positive plate to obtain the solid lithium battery.
Application example 4
A solid-state lithium battery is prepared by preparing the composite solid-state electrolyte of example 4 into a solution and then coating the solution on a nickel-cobalt-manganese ternary material (LiNi)0.5Co0.3Mn0.2O2) Forming a composite electrolyte membrane with the thickness of 200 mu m on the positive plate, volatilizing the solvent, and then pasting lithium cobaltate lithium titanate (Li) on the membrane4Ti5O12) And (4) preparing the negative plate to obtain the solid lithium battery.
Application example 5
A solid lithium battery is prepared by preparing the composite solid electrolyte of example 5 into a solution and then coating the solution on lithium iron phosphate (LiFePO)4) And (3) forming a composite electrolyte membrane with the thickness of 150 mu m on the positive plate, volatilizing the solvent, and then attaching a silicon-carbon composite negative electrode (Si/C) on the membrane to obtain the solid-state lithium battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a composite solid electrolyte is characterized by comprising the following steps:
dissolving at least one polymer of polycaprolactone and polycaprolactone derivatives and lithium salt in an organic solvent to obtain a first solution;
adding garnet oxide into the first solution, and uniformly mixing to obtain a second solution;
and casting and drying the second solution to obtain the composite solid electrolyte.
2. The method for preparing a composite solid electrolyte according to claim 1, wherein the percentage of each raw material component added is, based on 100% by mass of the obtained composite solid electrolyte:
10 to 90 percent of polymer;
5 to 80 percent of lithium salt;
garnet oxide 2-80%.
3. The method for preparing a composite solid electrolyte according to claim 1, wherein the polycaprolactone derivative is at least one selected from the group consisting of polystyrene-polycaprolactone, polyethylene oxide-polycaprolactone, polyvinylidene fluoride-polycaprolactone, polyacrylonitrile-polycaprolactone, perfluoropolyether-polycaprolactone, polymethacrylic acid-polycaprolactone, and polydimethylsiloxane-polycaprolactone;
the garnet oxide is selected from Li7La3Zr2O12、Li5La3Ta2O12、Li6BaLa2Ta2O12、Li6.4La3Zr1.4Ta0.6O12、Li6Sr0.5Ba0.5La2Ta2O12、Li3Tb3Te2O12、Li5La3Ta2O12、Li0.3La0.557TiO3、Li7La3Nb2O12、Li5La3Nb2O12、Li3Ln3Te2O12At least one of (a);
the lithium salt is selected from at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium hexafluorophosphate, lithium trifluoro methyl sulfonate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluoro oxalate borate and lithium bis (oxalate) borate.
4. The method for producing a composite solid electrolyte according to claim 1, wherein the organic solvent is at least one of acetonitrile, tetrahydrofuran, N-dimethylformamide, succinonitrile, methylene chloride, acetone, and N-methylpyrrolidone.
5. The method for preparing a composite solid electrolyte according to claim 1, wherein the drying treatment is carried out at a temperature of 45 ℃ to 150 ℃ for 12 hours to 72 hours.
6. The composite solid electrolyte is characterized by comprising the following components in percentage by mass of 100 percent:
10 to 90 percent of polymer;
5 to 80 percent of lithium salt;
garnet oxide 2% -80%;
the polymer is at least one of polycaprolactone and a polycaprolactone derivative.
7. The composite solid electrolyte of claim 6, wherein said polycaprolactone derivative is selected from at least one of polystyrene-polycaprolactone, polyethylene oxide-polycaprolactone, polyvinylidene fluoride-polycaprolactone, polyacrylonitrile-polycaprolactone, perfluoropolyether-polycaprolactone, polymethacrylic acid-polycaprolactone, polydimethylsiloxane-polycaprolactone;
the garnet oxide is selected from Li7La3Zr2O12、Li5La3Ta2O12、Li6BaLa2Ta2O12、Li6.4La3Zr1.4Ta0.6O12、Li6Sr0.5Ba0.5La2Ta2O12、Li3Tb3Te2O12、Li5La3Ta2O12、Li0.3La0.557TiO3、Li7La3Nb2O12、Li5La3Nb2O12、Li3Ln3Te2O12At least one of;
the lithium salt is selected from at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium hexafluorophosphate, lithium trifluoro methyl sulfonate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluoro oxalate borate and lithium bis (oxalate) borate.
8. A solid-state lithium battery comprising a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte between the positive electrode sheet and the negative electrode sheet, wherein the solid-state electrolyte is the composite solid-state electrolyte according to any one of claims 6 to 7.
9. The lithium solid state battery of claim 8, wherein the composite solid state electrolyte has a thickness of 5 μm to 4 cm.
10. A method of manufacturing a solid state lithium battery as claimed in any one of claims 8 to 9, comprising the steps of:
preparing the composite solid electrolyte into a solution, coating the composite solid electrolyte solution on the surface of the positive plate by a blade coating method, drying to obtain the positive plate attached with the composite solid electrolyte, and finally assembling the positive plate and the negative plate into a solid lithium battery;
or preparing the composite solid electrolyte into a solution, coating the composite solid electrolyte solution on the surface of the negative plate by a blade coating method, drying to obtain the negative plate attached with the composite solid electrolyte, and finally assembling the negative plate and the positive plate into the solid lithium battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258323A (en) * | 2018-01-30 | 2018-07-06 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of high specific energy solid lithium battery |
| CN108321355A (en) * | 2018-03-28 | 2018-07-24 | 中能中科（天津）新能源科技有限公司 | Lithium an- ode prefabricated component and preparation method thereof, lithium an- ode and lithium metal secondary cell |
| CN109390632A (en) * | 2017-08-08 | 2019-02-26 | 中国电子科技集团公司第十八研究所 | Preparation method of polymer solid-state battery with wide temperature range |
| CN109659606A (en) * | 2018-12-24 | 2019-04-19 | 燕山大学 | A kind of composite electrolyte membrane and preparation method thereof and lithium secondary battery |
-
2019
- 2019-10-18 CN CN201910993115.8A patent/CN110880620A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109390632A (en) * | 2017-08-08 | 2019-02-26 | 中国电子科技集团公司第十八研究所 | Preparation method of polymer solid-state battery with wide temperature range |
| CN108258323A (en) * | 2018-01-30 | 2018-07-06 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of high specific energy solid lithium battery |
| CN108321355A (en) * | 2018-03-28 | 2018-07-24 | 中能中科（天津）新能源科技有限公司 | Lithium an- ode prefabricated component and preparation method thereof, lithium an- ode and lithium metal secondary cell |
| CN109659606A (en) * | 2018-12-24 | 2019-04-19 | 燕山大学 | A kind of composite electrolyte membrane and preparation method thereof and lithium secondary battery |
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